Production of chlorotriazinyl



Patented July 19, 194

I1Q T$T PATENT V PRODUCTION F CHLOROTRiAZINYL NITRILES IngenuinHechenbleikner, Stamford, com.',- a;s :1: H a 7 Signor to AmericanCyanamid Company, New York, N. Y., a corporation of Maine No Drawing;

This invention relates to new and useful triazines, and moreparticularly to the production of new cyanoalkylaminochlorotriazines.

The cyanoalkylaminochlorotriazines of this invention may be representedby'the formula where X is chosen from the group consisting of hydrogen,alkyl, cycloalkyl, aryl, and cyano'alkyl,

and Y is cyanoalkyl. U v

Illustrative examples of the X, and Y groups which have the meaningsabove given are:

These cyanoalkylaminoclflorotriazines may be prepared in a number ofliquid media, and it is not necessary that the chlorotriazine for thereaction be completely in solution. However, if undissolvedchlorotriaz'ine is in suspensionit is desirable to have the solid in afinely divided state so as to be more easily available for reaction.

In the preparation'of the cyanoalkylaminochlorotriazines, hydrogenchloride is split off and Application January 13,"- 9 c 1 Serial No.572,753 v.

11 Claims. (01. zen-1249.15 a I? must .be removed fromithe 'reaction'f-This" is accomplished by adding Hclacceptors which include suchmaterials as'an excess of the amine used in'the reaction-,,sodiumbicarbonate-and sodium hydroxide. Other ,HCl-acceptors may be used withequal success, but for' the sake of economy and easy availability theabove are preferred. a

The cyanoalkylaminochlorotriazines herein described are useful inmanufacture of chemical intermediates, chemotherapeutic agents, dyes,insecticides, synthetic resins, plastics, and other materials in whichsubstituted triazines carrying cyanoalkylamino groups are-desirable. The

following examples? will illustrate the 'preparal tion of typicalcyanoalkylaminochlorotriazine materials hereindescribedlj .1EXAMPLEYILII 7 Preparation of 2,4-dichloro fi-cyanomethyl 1 qmz'no-1,3,5 -triazime,,;;. r i n-n onioN w Reactants Molar Ratio Oyanurlcchloride 1.0 A mfrme 13. 5 Glycinonitrile 1. 0 Sodium bicarbonate 1. 0Watcr 11. 0

The cyanuric chloride-is dissolved in acetone and the solutioncooled-to0-5 'C. The amino-- nitrile is added slowly to the-eyanuricchloride solution to keep the temperature at 05 When this addition iscomplete, theaqueous. suspension of sodium bicarbonate is added slowlywhile the temperature; is kept below 5 C. vCarbon dioxide is evolvedduring the addition of-'the sodium bicarbonate. The solution becomesclear and it is stirredfor 2;hours;a t 0?iC. -The reaction mixture isdilutedwith approximately an equal volume o wa e 1 p ecipi e, the, des ddizim- A ter, rec versmnd purifi ation the colorless crystallineso1id-mel-ts -at 178- l C. This compound has an irritating odor, and itis soluble in acetone, benzene, and hot water, but insoluble in hexane.

EXAMPLE 2 Preparation of2,4-dichloro-6-di-e-cyanoethylamino-1,3,5-tnaeine Reactants Molar RatioCyanuric chloride 71.0 A oetnne 13. Im nod prnninnih'ile 1 0 Sodiumbicarbonate 1 1.0 Water A 42. 0

The procedure for preparing this compound is the same as described inExample 1. After recovery and purification the melting point of thecolorless, odorless, crystalline solid is 212'-2l5 C.

This compound is soluble: in hot naphtha,alcohol, and benzene; butinsoluble in water...

Reectants Molar Ratio Cyanuric chloride l.0 Acetone 13.5ButyIaminnm-pfnnih-fla 1, 0 Sodium bicarbonate 1. 0 Water 42.0

V Molar Ratio sarcasm Sodium hydroxide Water 4 r a '1 a monomer c-sadded-tonic acetone solutionof the scenario c'hlride at a rate so that atem erature range or 30:35 o. is r'nai'ntained. After the additink theaifhinonitrile is complte the aqueous sdliin'i hydroiide is added slowlyat the same temperature range in order to dissolve the hydrochloride ofthe aminonitrilc and cause the reaction to go the completion. After thereaction mixture is diluted with a large volume of water, the desiredtriazine precipitates. After recovery and purification, the colorless,odorless, crystalline solid melts at -146" C. This compound is solublein most organic solvents, but insoluble in water.

EXAMPLE 5 Pre aration 0-; 2',4-dictum:athrigieranomethylamzno-LSj-triazine Gl- /CCl N Reactants Molar Ratio Cyanuricchloride l. 0 Acetone 10. 0 Phenylaminoacetonitrila 1. 0 Sodiumbicarbonate L 0 Water 7.0

The procedure for; preearing' tiiiscciriipourld is the same as thatdescribed in Example 1. After recovery and purification'the meltingpoint or the colorless, odorless, crystalline solid is 152-154 C. Thiscompound is: soluble in alcohol and benzene, but insoluble in water.

While the invention has been described with particular reference tospecific embodiments, it

is to be understood that it is not to be limited thereto but is to beconstrued broadly and re,- stricted solely by the scope oi the appendedclaims.

What is claimed:

1. A compound of the formula where X is chosenlfrorn the group.consisting of hydrogen, alkyl, eyeioaieyi, ai iyl, and cyanoalkyl, and Yis cyanoalliyl.

2. A method of preparing a compound of the formula V X-wNY where X ischosen from the group consisting of hydrogen, alkyl, cycloalkyl, aryl;and cyanoalkyl, and Y is cyanoalkyl, which comprises reacting cyanuricchloride with an amine of the formula where X and Y" have the andrecovering the-substituted1,3;5 triazine obtained, c

earrings above green, 7

3. 2,4-dichloro-6-cyanomethylamino-1,3,5-tri azine of the formula:

H-I -CHQCN N N 014 1 -0l 4. A method of preparing2,4-dichloro-6-cyanomethylamino-1,3,5-triazine which comprises reactingglycinonitrile with cyanuric chloride, and recovering the2,4-dichloro-6-cyanomethylamino-1,3,5-triazine obtained.

5. A method of preparing 2,4-dichloro-fi-cyanomethylamino-1,3,5-triazinewhich comprises reacting glycinonitrile with an aqueous acetone solutionof oyanuric chloride at a temperature below 35 C., and recovering the2,4-dich10ro-6- cyanomethylamino-1,3,5-triazine obtained.

6. 2,4-dich1oro-6-di- 13 -cyanoethylamino -1,3,5 triazine of theformula:

7. A method of preparing2,4-dioh1oro-6-di-pcyanoethylamino-1,3,5-triazine which comprisesreacting iminodipropioni trile with cyanuri-c chloride, and recoveringthe 2,4-dich1oro-6-di-flcyanoethylamino-1,3,5-triazine obtained.

8. A method of preparing2,4-dichloro-6-di-pcyanoethy1amino-1,3,5-triazine which comprisesreacting iminodipropionitrile with an aqueous I acetone solution ofcyanuric chloride at a temperature below 35 C., and recovering the 2,4-dichloro-G-dip cyanoethylamino -1,3,5-triazine obtained.

9. 2,4 dichloro 6 phenylcyanomethylamino- 1,3,5-triazine of the formula:

REFERENCES CITED The following referenlces are of record in the file ofthis patent:

Chem. Abstracts, vol. 31, p. 1010. Compte Rendue, vol. 203 (1936), pp.568-70.

